Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

Definitions

• the invention relates to thermosetting or air-drying paint binders based on copolymers of copolymerized units of (meth) acrylic acid esters, ⁇ , ⁇ -unsaturated carboxylic acids, N-methylol (meth) acrylic acid amides, optionally etherified, vinyltrialkylsilanes, reaction products of alkyl glycidyl ether and monocarboxylic acid and optionally vinyl and / or vinylidene aromatics and hydroxyalkyl (meth) acrylates or glycidyl (meth) acrylate, which can be further processed as water-thinnable paint binders after neutralization of the carboxyl groups.
• the copolymers can be used as paint binders for the production of coatings which, in addition to great mechanical strength and saponification stability, also have high gloss values and weather stability in an alkaline medium.
• the object of the present invention was to provide environmentally friendly paint binders which are suitable for the production of water-thinnable, high-solids coating compositions with extremely high saponification-stable storage stability in the presence of alkaline compounds, which, in the crosslinked state, also give extremely wash-resistant, high-gloss films with excellent mechanical properties and whose weathering behavior is so high that these binders can be used, for example, as an outermost protective layer in both pigmented and unpigmented form (for example for two-layer metallic coatings).
• compositions of the binders according to the invention were achieved by the compositions of the binders according to the invention.
• the copolymers can be prepared by copolymerizing the monomers a. - g. are carried out by customary methods, preference being given to free-radical polymerization in the melt or in solution.
• the polymerization can be carried out at temperatures of 70-160 ° C, preferably 100-150 ° C.
• the monomers a. - g. are incorporated into the copolymer resin in essentially the same ratios as are used for the polymerization, the copolymerized units being essentially randomly distributed.
• Preferred initiators for carrying out the free-radical polymerization are, for example, symmetrical aliphatic A zo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methyl-valeronitrile, 1,1'-azo-bis-cyclohexane-1-nitrile, and 2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, such as acetyl, propionyl or butyryl peroxide, bromine, nitro methyl or methoxy groups substituted benzoyl peroxides and lauroyl peroxide; symmetrical peroxydicarbonates, such as, for example, diethyl, diisopropyl, dicyclohexyl and dibenzyl peroxydicarbonate; tert-butyl peroctoate or tert-butylphenyl per-acetate and peroxycarbonates such as tert-butyl-N-
• the initiators can be used in amounts of 0.2-20.0% by weight, based on total monomers.
• Conventional regulators can also be used in the polymerization in amounts of 0.1-15% by weight, based on total monomers.
• inert solvents such as e.g. Ethanol, propanol, isopropanol, n- or iso-butanol, methyl ethyl ketone, toluene, xylene, butyl acetate, butyl glycol, etc. can be used.
• saturated lactams can also be used in addition to the solvents, the amounts of which, based on the copolymer, should not exceed 50% by weight.
• the saturated lactam can thus be present in the coating binder composed of copolymer and crosslinker in amounts of up to 50% by weight, based on the copolymer.
• the lactam can also be added to the copolymer after the polymerization.
• lactams used are saturated, they do not react with the monomers with copolymerization, but instead react with a crosslinking agent via their reactive NH group.
• the lactams used are essentially non-volatile and therefore remain in the film when hardened.
• Preferred lactams are 1-N-methyl-hexahydro-1,4-diazepion-3, CJ -dodecyllactam, ⁇ -butyrolactam, ⁇ -valerolactam, in particular e-caprolactam.
• the copolymers can be freed from volatile constituents at temperatures of 140-200 ° C. This can be done, for example, either under normal pressure in snake tube evaporators by blowing in an inert gas such as nitrogen or water vapor in quantities of 0.1 to 1 m 2 onto 1 kg of resin melt, or in a vacuum in evaporation apparatus such as falling film evaporators, thin-film evaporators, screw evaporators, flash evaporators or spray evaporators.
• an inert gas such as nitrogen or water vapor in quantities of 0.1 to 1 m 2 onto 1 kg of resin melt
• a vacuum in evaporation apparatus such as falling film evaporators, thin-film evaporators, screw evaporators, flash evaporators or spray evaporators.
• the average molecular weights and the molecular non-uniformities of the copolymer resins were determined with the aid of gel permeation chromatography (GPC) on styrenes with tetrahydrofuran as the eluent. After establishing a universal calibration relationship (according to Z. Grubisic, P. Rempp and H. Benoit, J. Polym. Sci. Part B, Polymer Letters 5 (1967) 754), the molecular weight averages Mw and Mn are determined from the distribution of the chromatograms.
• the copolymer contains built-in glycidyl groups, it can be modified by reaction with fatty acids, and air-drying binders can be obtained in the case of unsaturated fatty acids.
• copolymers of the invention are 5-50% by weight, preferably 15-45% by weight, based on the sum of the percentages of copolymer and aminoplast, in order to achieve optimum paint properties with aminoplast resins under the action of heat, optionally with the addition of conventional ones Cross-linked catalysts.
• Aldehyde condensation products such as melamine, urea and benzoguanamine may be mentioned as examples of suitable aminoplast resins.
• Formaldehyde is generally used as the aldehyde, although useful products are also obtained with other aldehydes such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde and furfurylaldehyde.
• the methylol groups of the aminoplasts can be etherified with saturated aliphatic monoalcohols with 1 to 4 carbon atoms. Melamine and urea resins are preferred.
• the carboxyl groups contained in the copolymer can be partially or completely neutralized in a preferred embodiment.
• the neutralization can take place in the presence or absence of the lactam and, if appropriate, further conventional solvents and in the presence or absence of the aminoplast resin.
• the degree of neutralization is preferably 30-100%, i.e. from 1 gram equivalent of carboxyl groups, 0.3 to 1 gram equivalents are neutralized. This results in a pH of the aqueous coating agent of between 5 and 10.
• the pH of the aqueous coating agent is preferably 7 to 9.
• Ammonia, mono- and polyamines can be used as neutralizing agents. Examples include: ammonia, ethylamine, diethylamine, triethylamine, trimethylamine, mono-, di- or triethanolamine, dimethylethanolamine, etc.
• Binders according to the invention from the copolymer with partially or completely neutralized carboxyl groups and aminoplast can be diluted with water, which optionally in the presence of organic solvents.
• Suitable organic solvents are, for example, alcohols with 1 to 4 carbon atoms, such as methanol, ethanol, n- and isopropanol, butanols; Essigklareester having 1 - 4 carbon atoms in the alcohol component, such as Essigklareethyl and butyl or ethyl glycol acetate, ethylene glycol mono-alkyl ether having 1 - 4 carbon - atoms in the alkyl radical such as ethylene, ethyl and butyl ether; aliphatic and alicyclic ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, lower ethers such as tetrahydrofuran or mixtures of the solvents mentioned.
• alcohols with 1 to 4 carbon atoms such as methanol, ethanol, n- and isopropanol, butanols
• Essigkladreester
• crosslinking of the binders according to the invention is the reaction with aminoplast resins
• they can also be cured with other crosslinking components to give coating films with a good level of properties.
• crosslinking components include epoxy compounds, polyisocyanates, phenoplasts such as resol resins and other crosslinking agents capable of crosslinking with the reactive groups of the binders according to the invention.
• the aqueous stoving lacquers (coating agents) obtained from the binders according to the invention after dilution with water, if appropriate in the presence of organic solvents, can contain white pigments, in particular titanium dioxide, in amounts of 20-200% by weight, based on the binder.
• white pigments in particular titanium dioxide
• inorganic or organic colored pigments in amounts of up to 90% by weight as well as fillers in amounts of likewise up to 90% by weight, leveling agent up to 10% by weight, waxes to increase the scratch resistance up to 10% by weight and customary curing catalysts up to 1% by weight .-%, each based on binder, may be contained in the coating agent.
• the coating compositions prepared in this way can be applied using the usual methods, e.g. by reverse roll coater, spraying, brushing and dipping or similar methods.
• Metals, glass, plastics, ceramic materials, preferably metals, are suitable as substrates to be coated or coated.
• the stoving lacquers are generally cured at temperatures of 80 - 250 ° C. It is sometimes advantageous to start curing at temperatures below 120 ° C and to complete at temperatures above 120 ° C.
• the coating compositions produced with the binders according to the invention result in coatings with excellent application data and of extremely high chemical and weather resistance.
• household appliances with metallic surfaces such as dishwashers, washing machines and refrigerators, can be coated with the aqueous stoving lacquers obtained from the binders according to the invention, since the coatings have a particularly high resistance to washing solutions and solvents, high gloss and excellent surface hardness.
• these binders are ideal for coating objects that are exposed to the weather.
• this also includes all types of transport, in particular automobiles, rail wagons, airplanes, containers and ships.
• 1029 g of ethyl glycol are placed in a glass vessel provided with a reflux condenser, heating, cooling and metering device and heated to 110.degree.
• a mixture of 120 g of the addition product of allyl glycidyl ether with ⁇ -ethylhexanoic acid (molar ratio 1: 1), 353 g of n-butyl acrylate, 805 g of styrene, 104 g of acrylic acid, 282 g of N-methoxymethylacrylic acid amide is then added at 100 ° C. , 60 g of vinyl trimethoxysilane and 10 g of mercaptoethanol are metered in.
• the copolymer consists of copolymerized units of 6.96% of the addition product of allyl glycidyl ether with ⁇ -ethylhexanoic acid, 20.5% n-butyl acrylate, 46.70% styrene, 6.00% acrylic acid, 16.36% N-methoxymethylacrylic acid amide and 3. 48% vinyl trimethoxysilane.
• the copolymer has an average molecular weight Mn of 4936 and a molecular inconsistency U of 1.30.
• the copolymer consists of copolymerized units of 10.44% of the addition product from allyl glycidyl ether with oL-ethylhexanoic acid, 20.5% n-butyl acrylate, 46.66% styrene, 6.00% acrylic acid and 16.40% N-methoxymethylacrylic acid amide. It has an average molecular weight Mn of 5210 and a molecular inconsistency U of 1.47.
• 1029 g of ethyl glycol are placed in a glass vessel provided with a reflux condenser, heating, cooling and metering device submitted and heated to 110 ° C.
• a mixture of 199 g of 2-hydroxyethyl methacrylate, 849 g of n-butyl acrylate, 522 g of styrene, 142 g of acrylic acid, 12 9 of vinyltriethoxysilane and 10 g of mercaptoethanol are then metered in over a period of 3 hours at 110 ° C.
• a mixture of 66 g is tert within a period of 4 h.
• Butyl peroctoate and 171 g of ethyl glycol were added dropwise.
• the solids content was determined by heating 1 g of resin solution on a metal lid of 7.5 cm in diameter in a layer thickness of approximately 50 ⁇ m to 80 ° C. in a forced-air drying cabinet.
• the copolymer itself consists of copolymerized units of 11.54% 2-hydroxyethyl methacrylate, 49.24% n-butyl acrylate, 30.29% styrene, 8.24% acrylic acid and 0.69% vinyl triethoxysilane.
• the result is a resin with an acid number of 28, measured in solution, a viscosity of 13 790 mPa.s and a solids content of approx. 59.9%.
• the copolymer itself consists of copolymerized units of 6.96% of the addition product allyl glycidyl ether with ⁇ -ethylhexanoic acid, 20.5% 2-ethylhexyl acrylate, 46.70% styrene, 6.00% acrylic acid, 3.48% vinyltrimethoxysilane, and 16.36 % N-methoxymethylacrylic acid amide.
• Example 1 With the exception of the monomer mixture, it was described as in Example 1.
• the following composition was used as the monomer mixture: 120 g of the addition product of allyl glycidyl ether with ⁇ -ethylhexanoic acid, 60 g of vinyl trimethoxysilane, 353 g of n-butyl acrylate, 805 g of methyl methacrylate, 104 g of acrylic acid, 282 g of N-methoxymethylacrylic acid amide and 10 g of mercaptoethanol.
• the result is a resin with an acid number of 28, measured in solution, a viscosity of 34,400 mPa.s and a solids content of approx. 59.6%.
• the copolymer itself consists of copolymerized units. 6.96% of the addition product from allyl glycidyl ether with ⁇ -ethylhexanoic acid, 3.48% vinyltrimethoxysilane, 20.47% n-butyl acrylate, 46.69% methyl methacrylate, 6.03 "% acrylic acid and 16 , 35% N-methoxymethylacrylic acid amide.
• Example 2 The procedure was as described in Example 1, with the exception of the monomer mixture.
• the following composition was used as the monomer mixture: 120 g of the addition product of allyl glycidyl ether with ⁇ -ethylhexanoic acid, 743 g of n-butyl acrylate, 60 g of vinyltrimethoxysilane, 415 g of styrene, 104 g of acrylic acid, 180 g of N-methoxymethylacrylic acid amide, 202 g of hydroxyethyl methacrylate and 10 g of mercury methyl methacrylate and 10 g of mercury methacrylate and 10 g of mercury methacrylate .
• the result is a resin with an acid number of 28, measured in solution, a viscosity of 4779 mPa.s and a solids content of approx. 59.4%.
• the copolymer itself consists of copolymerized units of 6.58% of the addition product from allyl glycidyl ether with ⁇ -ethylhexanoic acid, 40.73% n-butyl acrylate, 11.08%, hydroxyethyl methacrylate, 3.29% Vinyl trimethoxysilane, 22.75% styrene, 5.70% acrylic acid and 9.87% N-methoxymethylacrylic acid amide.
• the procedure was as described in Example 1, with the exception of the monomer mixture.
• the following composition was used as the monomer mixture: 120 g of the addition product consisting of allyl glycidyl ether with n-ethylhexanoic acid, 60 g of vinyl trimethoxysilane, 353 g of 2-ethylhexyl acrylate, 805 g of methyl methacrylate, 104 g of acrylic acid, 282 g of N-methoxymethyl acrylate amide and 10 g of mercaptoamide.
• the result is a resin with an acid number of 28, measured in solution, a viscosity of 44,200 mPa.s and a solids content of approx. 60.3%.
• the copolymer itself consists of copolymerized units of 6.96% of the addition product from allyl glycidyl ether with ⁇ -ethylhexanoic acid, 3.48% vinyltrimethoxysilane, 20.47% 2-ethylhexyl acrylate, 46.69% methyl methacrylate, 6.03% acrylic acid and 16.36 % N-methoxymethylacrylic acid amide.
• Example 1 With the exception of the monomer mixture, it was described as in Example 1.
• the following composition was used as the monomer mixture: 120 g of cinnamon alcohol, 60 g of vinyl trimethoxysilane, 353 g of 2-ethylhexyl acrylate, 805 g of styrene, 104 g of acrylic acid, 282 g of N-methoxymethylacrylic acid amide and 10 g of mercaptoethanol.
• the result is a resin with an acid number of 27, measured in solution, a viscosity of 13 455 mPa.s and a solids content of approx. 59.2%.
• the copolymer itself consists of copolymerized units of 6.96% cinnamon alcohol, 20.50% 2-ethylhexyl acrylate, 3.48% vinyl trimethoxysilane, 46.66% styrene, 6.00% acrylic acid and 16.40% N-methoxymethylacrylic acid amide.
• the procedure was as described in Example 1, with the exception of the monomer mixture.
• the following composition was used as the monomer mixture: 120 g of the addition product from allyl glycidyl ether with ⁇ -ethylhexanoic acid, 353 g of n-butyl acrylate, 60 g of vinyltriethoxysilane, 805 g of styrene; 104 g acrylic acid, 282 g N-methoxymethylacrylic acid amide and 10 g mercaptoethanol.
• the result is a resin with an acid number of 27, measured in solution, a viscosity of 16,320 mPa.s and a solids content of approx. 59.7%.
• the copolymer itself consists of copolymerized units. of 6.96% of the addition product allyl glycidyl ether with ⁇ -ethylhexanoic acid, 20.5% n-butyl acrylate, 3.48% vinyltriethoxysilane, 46th, 70% styrene, 6.00 acrylic acid and 16.36% N-methoxymethylacrylic acid amide.
• Example 1-7 and Comparative Experiments 1 and 2 100 parts of the copolymers described above (Examples 1-7 and Comparative Experiments 1 and 2) are neutralized with 4.34 parts of dimethylethanolamine and 7.84 parts of the neutralized copolymers are added with the addition of 27.12 parts of rutile-type titanium dioxide and 15. 46 parts of water regrind formulations for pearl mill grinding.
• the coating compositions prepared from the mill base formulations with the neutralized copolymer resins of Examples 1-7 and Comparisons 1 and 2 and with the non-neutralized copolymers of Examples 1-7 and Comparisons 1 and 2 are referred to as white varnishes 1-7 and Comparative 1,2 .
• the white paint obtained in each case was applied to zinc-phosphated steel sheets by spraying (dry film layer thickness approx. 25-30 gm) and 10 min. baked at 180 ° C in a circulating air dryer.
• the coated test sheets (thickness of the films 30 ⁇ m, baked for 10 minutes at 180 ° C., (then stored for 3 weeks at room temperature) were placed in a 0.2% aqueous solution of a commercially available detergent over a period of 4 hours at 95 ° C. based on pentasodium tripolyphosphate, sodium metasilicate, soda, oxyethylated nonylphenol (10 ethylene oxide units / mole phenol) and cyanuric acid chloride.

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• Polymers & Plastics (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)
• Drying Of Solid Materials (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Working-Up Tar And Pitch (AREA)

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• 1982
  • 1982-09-07 DE DE19823233171 patent/DE3233171A1/de not_active Withdrawn
• 1983
  • 1983-08-29 AT AT83108491T patent/ATE24929T1/de not_active IP Right Cessation
  • 1983-08-29 DE DE8383108491T patent/DE3369154D1/de not_active Expired
  • 1983-08-29 EP EP83108491A patent/EP0102606B1/fr not_active Expired
  • 1983-09-06 ES ES525401A patent/ES525401A0/es active Granted

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